CO2 Mixing Ratios Research Articles

Variations of O<sub>3</sub> and CO in summertime at a rural site near Beijing

Abstract. Large intra-season differences in mixing ratios of CO and O3 were detected at Miyun, a rural site north of Beijing, in summer 2006. Despite an increase in mean daytime mixing ratio of CO from 500 ppbv in June to 700 ppbv in July, mean daytime O3 dropped from 67 ppbv in June to 50 ppbv in July and August. The observed changes in CO and O3 are attributed to the influence of the summer monsoonal circulation that develops over the North China Plain in July. Photochemical production of O3 is reduced as a consequence of increased cloudiness during July and August, as indicated by the strong negative correlation observed between O3 and satellite observations of cloud optical depth, with cloudiness having little effect on CO. The analysis suggests a strategy for emission controls that could be implemented in an economically efficient manner to minimize the frequency of high levels of O3 during summer in Beijing.

Efficient calculation of intensity and polarization spectra in vertically inhomogeneous scattering and absorbing atmospheres

We present a method for the efficient calculation of moderate‐ and high‐resolution spectra of intensity and polarization in absorption bands. This linear‐k method explicitly accounts for the vertical distribution of the absorption optical thickness by using a linear approximation. It can be applied to any radiative transfer model that calculates the intensity (vector) and its derivatives with respect to the absorption optical thickness in different altitude layers of the model atmosphere. For the three spectral windows of the Orbiting Carbon Observatory (OCO), the error on the modeled intensity introduced by the linear‐k method is below 0.13% for the O2‐A band, below 0.06% in the weak CO2 band, and below 0.12% for the strong CO2 band, for an aerosol type dominated by coarse mode particles with an aerosol optical thickness (AOT) of 0.3 at the O2‐A band (the maximum AOT for which OCO retrievals are intended to be performed), and a typical aerosol height distribution with most aerosols located in the boundary layer. For these accuracies the computational effort is reduced by two orders of magnitude compared to line‐by‐line calculations. A sensitivity study with synthetic OCO measurements shows that the linear‐k method introduces a small error of 0.025–0.20 ppm on the retrieved profile weighted mean CO2 mixing ratio, for a boundary layer dominated aerosol distribution, and 0.050–0.50 ppm for an elevated aerosol layer between 5 and 6 km. In most cases the error is considerably smaller than the retrieval noise.

Where do fossil fuel carbon dioxide emissions from California go? An analysis based on radiocarbon observations and an atmospheric transport model

Characterizing flow patterns and mixing of fossil fuel‐derived CO2 is important for effectively using atmospheric measurements to constrain emissions inventories. Here we used measurements and a model of atmospheric radiocarbon (14C) to investigate the distribution and fluxes of atmospheric fossil fuel CO2 across the state of California. We sampled 14C in annual C3 grasses at 128 sites and used these measurements to test a regional model that simulated anthropogenic and ecosystem CO2 fluxes, transport in the atmosphere, and the resulting Δ14C of annual grasses (Δg). Average measured Δg levels in Los Angeles, San Francisco, the Central Valley, and the North Coast were 27.7 ± 20.0, 44.0 ± 10.9, 48.7 ± 1.9, and 59.9 ± 2.5‰, respectively, during the 2004–2005 growing season. Model predictions reproduced regional patterns reasonably well, with estimates of 27.6 ± 2.4, 39.4 ± 3.9, 46.8 ± 3.0, and 59.3 ± 0.2‰ for these same regions and corresponding to fossil fuel CO2 mixing ratios (Cf) of 13.7, 6.1, 4.8, and 0.3 ppm. Δg spatial heterogeneity in Los Angeles and San Francisco was higher in the measurements than in the predictions, probably from insufficient spatial resolution in the fossil fuel inventories (e.g., freeways are not explicitly included) and transport (e.g., within valleys). We used the model to predict monthly and annual transport patterns of fossil fuel‐derived CO2 within and out of California. Fossil fuel CO2 emitted in Los Angeles and San Francisco was predicted to move into the Central Valley, raising Cf above that expected from local emissions alone. Annually, about 21, 39, 35, and 5% of fossil fuel emissions leave the California airspace to the north, east, south, and west, respectively, with large seasonal variations in the proportions. Positive correlations between westward fluxes and Santa Ana wind conditions were observed. The southward fluxes over the Pacific Ocean were maintained in a relatively coherent flow within the marine boundary layer, while the eastward fluxes were more vertically dispersed. Our results indicate that state and continental scale atmospheric inversions need to consider areas where mixing ratio measurements are sparse (e.g., over the ocean to the south and west of California), transport within and across the marine boundary layer, and terrestrial boundary layer dynamics. Radiocarbon measurements can be very useful in constraining these estimates.

Lagrangian particle dispersion modeling for the high Alpine site Jungfraujoch

This study investigates the performance of a regional‐scale, time‐reversed Lagrangian particle dispersion model (LPDM) to model the atmospheric transport of inert trace gases to the Swiss high Alpine measurement station Jungfraujoch on a routine basis. The model is based on the operational dispersion model of the Swiss and German weather services (MeteoSwiss and DWD) and runs on analyzed meteorological fields from the weather prediction model Consortium for Small‐Scale Modeling (COSMO) of MeteoSwiss. On the basis of a sensitivity analysis, parameter values are derived which result in a reasonable compromise between accuracy and computational costs. The uncertainty associated with the choice of parameter values is estimated to be approximately 40% for modeled total times during which the air had ground contact before reaching Jungfraujoch and approximately 50% for modeled CO mixing ratios at Jungfraujoch. The release height of the particles has the most significant impact. Comparison of modeled CO mixing ratios with measured data over a 4‐month period from July to October 2004 reveals best agreement for a release height of 80 m above model ground. The correlation between 3‐hour averages of measured and modeled data results is r = 0.4. For daily mean values we find r = 0.5. Correlations are higher in autumn than in summer. Absolute values of modeled mixing ratios tend to be rather low but still within the range of measured data.

Vertical 2-μm Heterodyne Differential Absorption Lidar Measurements of Mean CO2 Mixing Ratio in the Troposphere

Abstract Vertical mean CO2 mixing ratio measurements are reported in the atmospheric boundary layer (ABL) and in the lower free troposphere (FT), using a 2-μm heterodyne differential absorption lidar (HDIAL). The mean CO2 mixing ratio in the ABL is determined using 1) aerosol backscatter signal and a mean derivative of the increasing optical depth as a function of altitude and 2) optical depth measurements from cloud target returns. For a 1-km vertical long path in the ABL, 2% measurement precision with a time resolution of 30 min is demonstrated for the retrieved mean CO2 absorption. Spectroscopic calculations are reported in details using new spectroscopic data in the 2-μm domain and the outputs of the fifth-generation Pennsylvania State University–National Center for Atmospheric Research Mesoscale Model (MM5). Then, using both aerosols in the ABL and midaltitude dense clouds in the free troposphere, preliminary HDIAL measurements of mean CO2 mixing ratio in the free troposphere are also presented. The 2-μm HDIAL vertical measurements are compared to ground-based and airborne in situ CO2 mixing ratio measurements and discussed with the atmospheric synoptic conditions.

A Case Study of CO2, CO and Particles Content Evolution in the Suburban Atmospheric Boundary Layer Using a 2-μm Doppler DIAL, a 1-μm Backscatter Lidar and an Array of In-situ Sensors

A network of remote and in-situ sensors was deployed in a Paris suburb in order to evaluate the mesoscale evolution of the daily cycle of CO2 and related tracers in the atmospheric boundary layer (ABL) and its relation to ABL dynamics and nearby natural and anthropogenic sources and sinks. A 2-μm heterodyne Doppler differential absorption lidar, which combines measurements of, (1) structure of the atmosphere, (2) radial velocity, and (3) CO2 differential absorption was a particularly unique element of the observational array. We analyse the differences in the diurnal cycle of CO, CO2, lidar reflectivity (a proxy for aerosol content) and H2O using the lidar, airborne measurements in the free troposphere and ground-based measurements made at two sites located few kilometres apart. We demonstrate that vertical mixing dominates the early morning drawdown of CO and aerosol content trapped in the former nocturnal layer but not the H2O and CO2 mixing ratio variations. Surface fluxes, vertical mixing and advection all contribute to the ABL CO2 mixing ratio decrease during the morning transition, with the relative importance depending on the rate and timing of ABL rise. We also show evidence that when the ABL is stable, small-scale (0.1-km vertical and 1-km horizontal) gradients of CO2 and CO are large. The results illustrate the complexity of inferring surface fluxes of CO2 from atmospheric budgets in the stable boundary layer.

Emission characteristic of ozone related trace gases at a semi-urban site in the Indo-Gangetic plain using inter-correlations

Measurements of surface O3, CO, NOx and light NMHCs were made during December 2004 at Hissar, a semi-urban site in the state of Haryana in north-west region of the Indo-Gangetic Plain (IGP). The night-time O3 values were higher when levels of CO, NO and NO2 were lower but almost zero values were observed during the episodes of elevated mixing ratios of CO (above 2000 ppbv) and NOx (above 50 ppbv). Slopes derived from linear fits of O3 versus CO and O3 versus NOx scatter plots were also negative. However, elevated levels of O3 were observed when CO and NOx were in the range of 200–300 ppbv and 20–30 ppbv, respectively. Slope of CO-NOx of about 33 ppbv/ppbv is much larger than that observed in the US and Europe indicating significant impact of incomplete combustion processes emitting higher CO and lesser NOx. Correlations and ratios of these trace gases including NMHCs show dominance of recently emitted pollutants mostly from biomass burning at this site.

Diurnal and vertical variability of the sensible heat and carbon dioxide budgets in the atmospheric surface layer

The diurnal and vertical variability of heat and carbon dioxide (CO2) in the atmospheric surface layer are studied by analyzing measurements from a 213 m tower in Cabauw (Netherlands). Observations of thermodynamic variables and CO2 mixing ratio as well as vertical profiles of the turbulent fluxes are used to retrieve the contribution of the budget terms in the scalar conservation equation. On the basis of the daytime evolution of turbulent fluxes, we calculate the budget terms by assuming that turbulent fluxes follow a linear profile with height. This assumption is carefully tested and the deviation from linearity is quantified. The budget calculation allows us to assess the importance of advection of heat and CO2 during day hours for three selected days. It is found that, under nonadvective conditions, the diurnal variability of temperature and CO2 is well reproduced from the flux divergence measurements. Consequently, the vertical transport due to the turbulent flux plays a major role in the daytime evolution of both scalars and the advection is a relatively small contribution. During the analyzed days with a strong contribution of advection of either heat or carbon dioxide, the flux divergence is still an important contribution to the budget. For heat, the quantification of the advection contribution is in close agreement with results from a numerical model. For carbon dioxide, we qualitatively corroborate the results with a Lagrangian transport model. Our estimation of advection is compared with traditional estimations based on the Net Ecosystem‐atmosphere Exchange (NEE).

Development of an OPO system at 1.57 μm for integrated path DIAL measurement of atmospheric carbon dioxide

Active remote sensing is a promising technique to close the gaps that exist in global measurement of atmospheric carbon dioxide sources, sinks and fluxes. Several approaches are currently under development. Here, an experimental setup of an integrated path differential absorption lidar (IPDA) is presented, operating at 1.57 μm using direct detection. An injection seeded KTP-OPO system pumped by a Nd:YAG laser serves as the transmitter. The seed laser is actively stabilized by means of a CO2 reference cell. The line-narrowed OPO radiation yields a high spectral purity, which is measured by means of a long path absorption cell. First measurements of diurnal variations of the atmospheric CO2 mixing ratio using a topographic target were performed and show good agreement compared to simultaneously taken measurements of an in situ device. A further result is that the required power reference measurement of each laser pulse in combination with the spatial beam quality is a critical point of this method. The system described can serve as a testbed for further investigations of special features of the IPDA technique.

Influence of Ammonia and Carbon Dioxide on the Sorption of a Basic Organic Pollutant to Carpet and Latex-Painted Gypsum Board

Sorptive interactions with indoor surfaces strongly influence indoor exposure to organic pollutants. Adsorption itself may be influenced by indoor levels of common indoor gases such as CO2, NH3, and H2O. We quantified sorption characteristics of trimethylamine (TMA) on carpet and painted wallboard, while challenging the surface with gas-phase CO2, NH3 and H2O. We show that the capacity of the carpet to sorb TMA, doubles when the CO2 mixing ratio is increased from 0 to 1000 ppm CO2 at 90% relative humidity. In contrast, NH3 decreases the surface capacity of both carpet and latex paint. Sorption of TMA to these indoor materials is primarily caused by interactions at one or more interfaces. Dissolution of TMA and aqueous acid-base chemistry appear to also contribute to the overall sorptive capacity of carpet at high relative humidity. The reduction in the distribution coefficient, k(e), in the presence of NH3 is explained by competition between TMA and NH3 molecules for sites on the substrates at low-to-medium relative humidity conditions.

High-resolution spectroscopy of Venus: Detection of OCS, upper limit to H 2S, and latitudinal variations of CO and HF in the upper cloud layer

Venus was observed at 2.4 and 3.7 μm with a resolving power of 4 × 10 4 using the long-slit high-resolution spectrograph CSHELL at NASA IRTF. The observations were made along a chord that covered a latitude range of ± 60° at a local time near 8:00. The continuous reflectivity and limb brightening at 2.4 μm are fitted by the clouds with a single scattering albedo 1 − a = 0.01 and a pure absorbing layer with τ = 0.09 above the clouds. The value of 1 − a agrees with the refractive index of H 2SO 4 (85%) and the particle radius of 1 μm. The absorbing layer is similar to that observed by the UV spectrometer at the Pioneer Venus orbiter. However, its nature is puzzling. CO 2 was measured using its R32 and R34 lines. The retrieved product of the CO 2 abundance and airmass is constant at 1.9 km-atm along the instrument slit in the latitude range of ± 60°. The CO mixing ratio (measured using the P21 line) is rather constant at 70 ppm, and its variations of ∼10% may be caused by atmospheric dynamics. The observed value is higher than the 50 ppm retrieved previously from a spectrum of the full disk, possibly, because of some downward extension of the mesospheric morningside bulge of CO. The observations of the HF R3 line reveal a constant HF mixing ratio of 3.5 ± 0.5 ppb within ± 60° of latitude, which is within the scatter in the previous measurements of HF. OCS has been detected for the first time at the cloud tops by summing 17 lines of the P-branch. The previous detections of OCS refer to the lower atmosphere at 30–35 km. The retrieved OCS mixing ratio varies with a scale height of 1 to 3 km. The mean OCS mixing ratio is ∼2 ppb at 70 km and ∼14 ppb at 64 km. Vertical motions in the atmosphere may change the OCS abundance. The detected OCS should significantly affect Venus' photochemistry. A sensitive search for H 2S using its line at 2688.93 cm −1 results in a 3 sigma upper limit of 23 ppb, which is more restrictive than the previous limit of 100 ppb.

Venus upper atmospheric CO, temperature, and winds across the afternoon/evening terminator from June 2007 JCMT sub-millimeter line observations

The Venus mesosphere constitutes a highly variable transition region between the zonal rotation of the lower atmosphere and the diurnal circulation of the upper atmosphere. It further serves as the primary photochemical region of the Venus atmosphere. We obtained James Clerk Maxwell Telescope (JCMT, Mauna Kea Hawaii) sub-millimeter line observations of mesospheric 12CO and 13CO during coordinated space (MESSENGER and Venus Express) and ground-based observations of Venus in June of 2007. Such CO spectra line measurements support temperature, CO mixing ratio, and wind retrievals over the 80–110 km altitude range, encompassing the upper mesosphere and lower thermosphere of Venus. Five-point beam integrations were obtained across the observed Venus disk, allowing distinction of afternoon (noon to 6 p.m.) versus evening (6 p.m. to midnight) local times and northern (0–60N) versus southern (0–60S) latitudes. Distinctive diurnal variations (noon to midnight) are retrieved for both temperatures above 95 km and CO mixing ratios above 85 km altitudes. Separate CO line maps obtained on (UT) June 2, 3, 6, and 11 indicate moderate daily variability in afternoon and evening CO mixing ratios (20–50%) and temperatures (5–10 K). Average Venus mesospheric temperatures over this period were 10 K warmer than returned from 1978 to 1979 Pioneer Venus or 2000–01 sub-millimeter measurements, without evidence for the very large temperature inversions indicated by Venus Express SPICAV measurements at 90–100 km altitudes (Bertaux, J.L., Vandaele, A.-C., Korablev, O., Villard, E., Fedorova, A., Fussen, D., Quémerais, E., Belyaev, D., Mahieux, A., Montmessin, F., Muller, C., Neefs, E., Nevejans, D., Wilquet, V., Dubois, J.P. Hauchecorne, A., Stepanov, A., Vinogradov, I., Rodin, A., Bertaux, J.-L., Nevejans, D., Korablev, O., Montmessin, F., Vandaele, A.-C., Fedorova, A., Cabane, M., Chassefière, E., Chaufray, J.Y., Dimarellis, E., Dubois, J.P., Hauchecorne, A., Leblanc, F., Lefèvre, F., Rannou, P., Quémerais, E., Villard, E., Fussen, D., Muller, C., Neefs, E., Van Ransbeeck, E., Wilquet, V., Rodin, A., Stepanov, A., Vinogradov, I., Zasova, L., Forget, F., Lebonnois, S., Titov, D., Rafkin, S., Durry, G., Gérard, J.C., Sandel, B., 2007. A warm layer in Venus’ cryosphere and high-altitude measurements of HF, HCl, H 2O and HDO. Nature 450, 646–649). Measured Doppler shifts associated with June 2 and 11 12CO line center absorptions indicate nearly supersonic (200 m/s, Mach 1) afternoon-to-evening (retrograde) circulation; composed of additive subsolar-to-antisolar (SSAS) and zonal retrograde wind components, which are not separable due to the particular observational geometry.

Sources of particulate matter in the northeastern United States in summer: 1. Direct emissions and secondary formation of organic matter in urban plumes

Ship and aircraft measurements of aerosol organic matter (OM) and water‐soluble organic carbon (WSOC) were made in fresh and aged pollution plumes from major urban areas in the northeastern United States in the framework of the 2004 International Consortium for Atmospheric Research on Transport and Transformation (ICARTT) study. A large part of the variability in the data was quantitatively described by a simple parameterization from a previous study that uses measured mixing ratios of CO and either the transport age or the photochemical age of the sampled air masses. The results suggest that OM was mostly due to secondary formation from anthropogenic volatile organic compound (VOC) precursors in urban plumes. Approximately 37% of the secondary formation can be accounted for by the removal of aromatic precursors using newly published particulate mass yields for low‐NOx conditions, which are significantly higher than previous results. Of the secondary formation, 63% remains unexplained and is possibly due to semivolatile precursors that are not measurable by standard gas chromatographic methods. The observed secondary OM in urban plumes may account for 35% of the total source of OM in the United States and 8.5% of the global OM source. OM is an important factor in climate and air quality issues, but its sources and formation mechanisms remain poorly quantified.

Air pollution during the 2003 European heat wave as seen by MOZAIC airliners

Abstract. This study presents an analysis of both MOZAIC profiles above Frankfurt and Lagrangian dispersion model simulations for the 2003 European heat wave. The comparison of MOZAIC measurements in summer 2003 with the 11-year MOZAIC climatology reflects strong temperature anomalies (exceeding 4°C) throughout the lower troposphere. Higher positive anomalies of temperature and negative anomalies of both wind speed and relative humidity are found for the period defined here as the heat wave (2–14 August 2003), compared to the periods before (16–31 July 2003) and after (16–31 August 2003) the heat wave. In addition, Lagrangian model simulations in backward mode indicate the suppressed long-range transport in the mid- to lower troposphere and the enhanced southern origin of air masses for all tropospheric levels during the heat wave. Ozone and carbon monoxide also present strong anomalies (both ~+40 ppbv) during the heat wave, with a maximum vertical extension reaching 6 km altitude around 11 August 2003. Pollution in the planetary boundary layer (PBL) is enhanced during the day, with ozone mixing ratios two times higher than climatological values. This is due to a combination of factors, such as high temperature and radiation, stagnation of air masses and weak dry deposition, which favour the accumulation of ozone precursors and the build-up of ozone. A negligible role of a stratospheric-origin ozone tracer has been found for the lower troposphere in this study. From 29 July to 15 August 2003 forest fires burnt around 0.3×106 ha in Portugal and added to atmospheric pollution in Europe. Layers with enhanced CO and NOy mixing ratios, advected from Portugal, were crossed by the MOZAIC aircraft in the free troposphere over Frankfurt. A series of forward and backward Lagrangian model simulations have been performed to investigate the origin of anomalies during the whole heat wave. European anthropogenic emissions present the strongest contribution to the measured CO levels in the lower troposphere (near 30%). This source is followed by Portuguese forest fires which affect the lower troposphere after 6 August 2003 and even the PBL around 10 August 2003. The averaged biomass burning contribution reaches 35% during the affected period. Anthropogenic CO of North American origin only marginally influences CO levels over Europe during that period.

Interactions between boreal wildfire and urban emissions

A suite of particulate, gaseous and meteorological measurements during the Pittsburgh Supersite experiment were used to characterize the impact of the 2002 Quebec wildfires on pollutant concentrations and physical and chemical processes dominant in the region. Temporal trends in the number distribution of wildfire particles (isolated using Rapid Single‐ultrafine‐particle Mass Spectrometry data) combined with CO, NOx and O3 mixing ratios identified two separate periods (Periods I and II) when the measurement site was directly impacted by plumes of relatively unprocessed wildfire emissions; i.e., increases in primary ultrafine wildfire particles, CO and NOx concomitant with a decrease in O3 from intraplume NOx titration. Carbonaceous particle number distributions predominantly associated with vehicular emissions, PM2.5 sulfate mass concentration and SO2 mixing ratio resolved individual components of local and regional sources. Single particle signatures indicated a period of intense atmospheric processing following Period II that caused rapid growth of the ultrafine mode due to simultaneous sulfate and secondary organic mass accumulation, resulting in significant changes to particle physical and chemical properties. Particle growth was concurrent with large increases in O3 and maxima in incoming solar radiation and ambient temperature and is posited to have occurred in situ as the air mass, containing a mixture of urban and wildfire emissions, was advected past the site. In total, the current work demonstrates significant added severity for pollution episodes in an area already burdened by large anthropogenic emission rates due to the impact of the 2002 Quebec wildfires. High levels of atmospheric processing increased sulfate accumulation and SOA formation and brought PM2.5 mass concentrations close to, and O3 mixing ratios in excess of, the National Ambient Air Quality Standards. Projections of increasing wildfire activity under a warming climate may increase the frequency and severity of such events.

Characteristics of the atmospheric CO2 signal as observed over the conterminous United States during INTEX‐NA

High resolution in situ measurements of atmospheric CO2 were made from the NASA DC‐8 aircraft during the Intercontinental Chemical Transport Experiment–North America (INTEX‐NA) campaign, part of the wider International Consortium for Atmospheric Research on Transport and Transformation (ICARTT). During the summer of 2004, eighteen flights comprising 160 h of measurements were conducted within a region bounded by 27 to 53°N and 36 to 139°W over an altitude range of 0.15 to 12 km. These large‐scale surveys provided the opportunity to examine the characteristics of the atmospheric CO2 signal over sparsely sampled areas of North America and adjacent ocean basins. The observations showed a high degree of variability (≤18%) due to the myriad source and sink processes influencing the air masses intercepted over the INTEX‐NA sampling domain. Surface fluxes had strong effects on continental scale concentration gradients. Clear signatures of CO2 uptake were seen east of the Mississippi River, notably a persistent CO2 deficit in the lowest 2–3 km. When combining the airborne CO2 measurements with LANDSAT and MODIS data products, the lowest CO2 mixing ratios observed during the campaign (337 ppm) were tied to mid‐continental agricultural fields planted in corn and soybeans. We used simultaneous measurements of CO, O3, C2Cl4, C2H6, C2H2 and other unique chemical tracers to differentiate air mass types. Coupling these distinct air mass chemical signatures with transport history permitted identification of convection, stratosphere‐troposphere exchange, long‐range transport from Eastern Asia, boreal wildfires, and continental outflow as competing processes at multiple scales influencing the observed concentrations. Our results suggest these are important factors contributing to the large‐scale distribution in CO2 mixing ratios thus these observations offer new constraints in the computation of the North American carbon budget.

Observations of CO on Saturn and Uranus at millimeter wavelengths: new upper limit determinations

Aims. We observed Saturn and Uranus at CO millimetric line wavelengths in order to better constrain the origin of CO in the atmospheres of these planets. CO sources can be either of internal or of external origin. Methods. We recorded broad multi-band spectra of Saturn and Uranus at the frequencies of the J = 1 → 0a ndJ = 2 → 1 CO lines. Results. As we do not detect any CO line in the spectra, we derive new upper limits of the abundance of CO in the atmospheres of Saturn and Uranus. The value we obtain for Saturn (6.3 × 10 −8 , restricted to the stratosphere) is larger than the value of the CO mixing ratio in the external origin model used. New observations with higher sensitivity and/or longer observing time should enable us to determine the CO external source strength. The upper limit we derive on Uranus is slightly lower (2.7 × 10 −8 , restricted to the stratosphere) than the value derived from an early observation of CO on Uranus, at infrared wavelength. As the fluorescence model used then did not take scattering effects into account, we suggest that the value could be overestimated.

Vertical mixing in atmospheric tracer transport models: error characterization and propagation

Abstract. Imperfect representation of vertical mixing near the surface in atmospheric transport models leads to uncertainties in modelled tracer mixing ratios. When using the atmosphere as an integrator to derive surface-atmosphere exchange from mixing ratio observations made in the atmospheric boundary layer, this uncertainty has to be quantified and taken into account. A comparison between radiosonde-derived mixing heights and mixing heights derived from ECMWF meteorological data during May–June 2005 in Europe revealed random discrepancies of about 40% for the daytime with insignificant bias errors, and much larger values approaching 100% for nocturnal mixing layers with bias errors also exceeding 50%. The Stochastic Time Inverted Lagrangian Transport (STILT) model was used to propagate this uncertainty into CO2 mixing ratio uncertainties, accounting for spatial and temporal error covariance. Average values of 3 ppm were found for the 2 month period, indicating that this represents a large fraction of the overall uncertainty. A pseudo data experiment shows that the error propagation with STILT avoids biases in flux retrievals when applied in inversions. The results indicate that flux inversions employing transport models based on current generation meteorological products have misrepresented an important part of the model error structure likely leading to biases in the estimated mean and uncertainties. We strongly recommend including the solution presented in this work: better, higher resolution atmospheric models, a proper description of correlated random errors, and a modification of the overall sampling strategy.

First ground‐based FTIR observations of the seasonal variation of carbon monoxide in the tropics

We present the first ground‐based solar absorption Fourier Transform Infrared (FTIR) spectrometric measurements in the inner tropics over several years. The FTIR observations agree well with satellite data from the MOPITT instrument. MATCH‐MPIC model simulations reproduce the mean vertical structure of the FTIR observations. The model is generally not able to reproduce the extreme enhancements seen during the specific biomass burning events by both observation instruments. Nevertheless, the model indicates that beyond the background source of CO from methane oxidation, the main contributions to the CO mixing ratios are the episodic convective injection of NMHCs and CO from South American biomass burning into the upper troposphere, along with long range transport of African biomass burning CO, particularly during spring. In future studies with more extensive observed time series, observations such as these will be valuable for evaluating ongoing improvements in global chemistry transport models.

An idealized model of the one-dimensional carbon dioxide rectifier effect

The net flux of carbon dioxide (CO2) from the land surface into the atmospheric boundary layer has a diurnal cycle. Drawdown of CO2 occurs during daytime photosynthesis, and return of CO2 to the atmosphere occurs during night. Even when the net diurnal-average surface flux vanishes, the diurnal-average profile of atmospheric CO2 mixing ratio is usually not vertically uniform. This is because of the diurnal rectifier effect, by which atmospheric vertical transport and the surface flux conspire to produce a surplus of CO2 near the ground and a deficit aloft.This paper constructs an idealized, 1-D, eddy-diffusivity model of the rectifier effect and provides an analytic series solution. When non-dimensionalized, the intensity of the rectifier effect is related solely to a single ‘rectifier parameter’. Given this model’s governing equation and boundary conditions, we prove that the existence of the rectifier effect is related to the correlation of CO2 gradient and transport, and also to the day–night symmetry of transport.The rectifier-induced near-surface CO2 surplus ought to be included in inverse calculations that use near-surface CO2 mixing ratio to infer land–surface sources and sinks of carbon. Such inverse modeling is facilitated by our model’s simplicity. To illustrate, we use a 1-D inverse calculation to infer the amplitude of diurnal CO2 surface flux.